In situ drop-coated BaZr0.1Ce0.7Y0.2O3−δ electrolyte-based proton-conductor solid oxide fuel cells with a novel layered PrBaCuFeO5+δ cathode

In order to develop a simple and cost-effective route to fabricate proton-conductor intermediate-temperature SOFCs, a dense BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY) electrolyte was fabricated on a porous anode by in situ drop-coating. The PrBaCuFeO_5+δ (PBCF) composite oxide with layered perovskite structure was synthesized by auto ignition process and examined as a novel cathode for proton-conductor IT-SOFCs. The single cell, consisting of PBCF/BZCY/NiO-BZCY structure, was assembled and tested from 600 to 700 °C with humidified hydrogen (∼3% H₂O) as the fuel and the static air as the oxidant. An open-circuit potential of 1.01 V and a maximum power density of 445 mW cm⁻² at 700 °C were obtained for the single cell. A relatively low interfacial polarization resistance of 0.15 Ω cm² at 700 °C indicated that the PBCF is a promising cathode for proton-conductor IT-SOFCs.     

A cobalt-free SrFe0.9Sb0.1O3−δ cathode material for proton-conducting solid oxide fuel cells with stable BaZr0.1Ce0.7Y0.1Yb0.1O3−δ electrolyte

A cobalt-free cubic perovskite oxide SrFe_0.9Sb_0.1O_3−δ (SFSb) is investigated as a novel cathode for proton-conducting solid oxide fuel cells (H-SOFCs). XRD results show that SFSb cathode is chemically compatible with the electrolyte BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3−δ (BZCYYb) for temperatures up to 1000 °C. Thin proton-conducting BZCYYb electrolyte and NiO-BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3−δ (NiO-BZCYYb) anode functional layer are prepared over porous anode substrates composed of NiO-BZCYYb by a one-step dry-pressing/co-firing process. Laboratory-sized quad-layer cells of NiO-BZCYYb/NiO-BZCYYb/BZCYYb/SFSb are operated from 550 to 700 °C with humidified hydrogen (∼3% H₂O) as fuel and the static air as oxidant. An open-circuit potential of 0.996 V, maximum power density of 428 mW cm⁻², and a low electrode polarization resistance of 0.154 Ω cm² are achieved at 700 °C. The experimental results indicate that the cobalt-free SFSb is a promising candidate for cathode material for H-SOFCs.     

Electrochemical performance of BaZr0.1Ce0.7Y0.1Yb0.1O3−δ electrolyte based proton-conducting SOFC solid oxide fuel cell with layered perovskite PrBaCo2O5+δ cathode

BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3−δ (BZCYYb) exhibits adequate protonic conductivity as well as sufficient chemical and thermal stability over a wide range of SOFC operating conditions, while layered perovskite PrBaCo₂O_5+δ (PBCO) has advanced electrochemical properties. This research fully takes advantage of these advanced properties and develops a novel protonic ceramic membrane fuel cell (PCMFC) of Ni-BZCYYb|BZCYYb|PBCO. The performance of the button cell was tested under intermediate-temperature range from 600 to 700 °C with humified H₂ (∼3% H₂O) as fuel and ambient air as oxidant. The results show that the open circuit potential of 0.983 V and the maximal power density of 490 mW cm⁻² were achieved at 700 °C. By co-doping barium zirconate-cerate with Y and Yb, the conductivity of electrolyte was significantly improved. The polarization processes of the button cell were characterized using the complicated electrochemical impedance spectroscopy technique. The results indicate that the polarization resistances contributed from both charge migration processes and mass transfer processes increase with decreasing cell voltage loads. However the polarization resistance induced by mass transfer processes is negligible in the studied button cell.     

A cobalt-free Sm0.5Sr0.5FeO3−δ–BaZr0.1Ce0.7Y0.2O3−δ composite cathode for proton-conducting solid oxide fuel cells

A cobalt-free Sm_0.5Sr_0.5FeO_3−δ–BaZr_0.1Ce_0.7Y_0.2O_3−δ (SSF–BZCY) was developed as a composite cathode material for proton-conducting solid oxide fuel cells (H-SOFC) based on proton-conducting electrolyte of stable BZCY. The button cells of Ni-BZCY/BZCY/SSF–BZCY were fabricated and tested from 550 to 700 °C with humidified H₂ (～3% H₂O) as a fuel and ambient oxygen as oxidant. An open-circuit potential of 1.024 V, maximum power density of 341 mW cm⁻², and a low electrode polarization resistance of 0.1 Ω cm² were achieved at 700 °C. The experimental results indicated that the SSF–BZCY composite cathode is a good candidate for cathode material.     

BaZr0.1Ce0.7Y0.1Yb0.1O3−δ as highly active and carbon tolerant anode for direct hydrocarbon solid oxide fuel cells

BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3−δ (BZCYYb) perovskite is synthesized and examined as an alternative anode material for intermediate temperature solid oxide fuel cells (IT-SOFCs) based on direct hydrocarbon fuels, using polarization and electrochemical impedance spectroscopy techniques. Single-phased BZCYYb anode shows an excellent activity for both hydrogen and methane oxidation reactions, achieving a polarization resistance of 0.25 and 0.93 Ω cm², and overpotential of 20 and 202 mV at 100 mA cm⁻² and 750 °C in wet H₂ (3% H₂O/97% H₂) and wet CH₄ (3% H₂O/97% CH₄), respectively. The electrocatalytic activity of BZCYYb anodes is significantly higher than that of the (La,Sr)(Cr,Mn)O₃ anodes as reported in the literature. Furthermore, BZCYYb exhibits excellent resistance to carbon deposition. The present study demonstrates that BZCYYb perovskite is a promising alternative anode material for direct hydrocarbon fuels based SOFCs.     

Enhanced sinterability of BaZr0.1Ce0.7Y0.1Yb0.1O3−δ by addition of nickel oxide

The effect of nickel oxide addition on the sintering behavior and electrical properties of BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3−δ (BZCYYb) as an electrolyte for solid oxide fuel cells was systematically studied. Results suggest that the addition of a small amount (∼1 wt%) of NiO to BZCYYb greatly promoted densification, achieving ∼96% of the theoretical density after sintering at 1350 °C in air for 3 h (reducing the sintering temperature by ∼200 °C). Further, a sample sintered at 1450 °C for 3 h showed high open circuit voltages (OCVs) when used as the electrolyte membrane to separate the two electrodes under typical SOFC operating conditions, indicating that the electrical conductivity of the electrical conductivity of the BZCYYb was not adversely affected by the addition of ∼1 wt% NiO.     

Fabrication and characterization of anode-supported micro-tubular solid oxide fuel cell based on BaZr0.1Ce0.7Y0.1Yb0.1O3−δ electrolyte

Anode-supported micro-tubular solid oxide fuel cells (SOFCs) based on a proton and oxide ion mixed conductor electrolyte, BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3−δ (BZCYYb), have been fabricated using phase inversion and dip-coating techniques with a co-firing process. The single cell is composed of NiO-BZCYYb anode, BZCYYb electrolyte and La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF)-BZCYYb cathode. Maximum power densities of 0.08, 0.15, and 0.26 W cm⁻² have been obtained at 500, 550 and 600 °C, respectively, using H₂ as fuel and ambient air as oxidant.     

A novel cobalt-free layered GdBaFe2O5+δ cathode for proton conducting solid oxide fuel cells

While cobalt-containing perovskite-type cathode materials facilitate the activation of oxygen reduction, they also suffer from problems like poor chemical stability in CO₂ and high thermal expansion coefficients. In this research, a cobalt-free layered GdBaFe₂O_5+δ (GBF) perovskite was developed as a cathode material for protonic ceramic membrane fuel cells (PCMFCs) based on proton conducting electrolyte of stable BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY7). The button cells of Ni-BZCY7|BZCY7|GBF were fabricated and characterized using complex impedance technique from 600 to 700 °C. An open-circuit potential of 1.007 V, maximum power density of 417 mW cm⁻², and a low electrode polarization resistance of 0.18 Ω cm² were achieved at 700 °C. The results indicate that layered GBF perovskite is a good candidate for cobalt-free cathode material, while the developed Ni-BZCY7|BZCY7|GBF cell is a promising functional material system for solid oxide fuel cells.     

Optimization of BaZr0.1Ce0.7Y0.2O3−δ-based proton-conducting solid oxide fuel cells with a cobalt-free proton-blocking La0.7Sr0.3FeO3−δ-Ce0.8Sm0.2O2−δ composite cathode

BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY)-based proton-conducting solid oxide fuel cells (H-SOFC) with a cobalt-free proton-blocking La_0.7Sr_0.3FeO_3−δ-Ce_0.8Sm_0.2O_2-δ (LSF-SDC) composite cathode were fabricated and evaluated. The effect of firing temperature of the cathode layer on the chemical compatibility, microstructure of the cathode and cathode-electrolyte interface, as well as electrochemical performance of single cells was investigated in detail. The results indicated that the cell exhibited the most desirable performance when the cathode was fired at 1000 °C; moreover, at the same firing temperature, the power performance had the least temperature dependence. With humidified hydrogen (∼2% H₂O) as the fuel and ambient air as the oxidant, the polarization resistance of the cell with LSF-SDC cathode fired at 1000 °C for 3 h was as low as 0.074 Ω cm² at 650 °C after optimizing microstructures of the anode and anode-electrolyte interface, and correspondingly the maximum power density achieved as high as 542 mW cm⁻², which was the highest power output ever reported for BZCY-based H-SOFC with a cobalt-free cathode at 650 °C.     

Novel layered perovskite oxide PrBaCuCoO5+δ as a potential cathode for intermediate-temperature solid oxide fuel cells

A novel layered perovskite oxide PrBaCuCoO_5+δ (PBCCO) is employed as a potential cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs). Thermal expansion and electrochemical performance on samarium-doped ceria (SDC) electrolyte are evaluated. The thermal expansion coefficient (TEC) of PrBaCuCoO_5+δ (PBCCO) is close to that of SDC electrolyte and electrical conductivity of PrBaCuCoO_5+δ (PBCCO) reaches the general required value of cathode material. Symmetrical electrochemical cell with the configuration of PrBaCuCoO_5+δ (PBCCO)/SDC/PrBaCuCoO_5+δ (PBCCO) applied for the impedance studies, the area specific resistance of PrBaCuCoO_5+δ (PBCCO) cathode is as low as 0.047 Ω cm² at 700 °C. A maximum power density of 791 mW cm⁻² is obtained at 700 °C for the single cell consisting of PrBaCuCoO_5+δ (PBCCO)/SDC/NiO-SDC. Preliminary results indicate that PrBaCuCoO_5+δ (PBCCO) is especially promising as a cathode for IT-SOFCs.     

SrCo1−xSbxO3−δ perovskite oxides as cathode materials in solid oxide fuel cells

The SrCo_1−xSb_xO_3−δ (x = 0.05, 0.1, 0.15 and 0.2) system was tested as possible cathode for solid oxide fuel cells (SOFCs). X-ray diffraction results show the stabilization of a tetragonal P4/mmm structure with Sb contents between x = 0.05 and x = 0.15. At x = 0.2 a phase transition takes place and the material is defined in the cubic Pm-3m space group. In comparison with the undoped hexagonal SrCoO₃ phase, the obtained compounds present high thermal stability without abrupt changes in the expansion coefficient. In addition, a great enhancement of the electrical conductivity was observed at low and intermediate temperatures (T ≤ 800 °C). The sample with x = 0.05 displays the highest conductivity value that reaches 500 S cm⁻¹ at 400 °C and is over 160 S cm⁻¹ in the usual working conditions of a cathode in SOFC (650-900 °C). Moreover, the impedance spectra of the SrCo_1−xSb_xO_3−δ/Ce_0.8Nd_0.2O_2−δ/SrCo_1−xSb_xO_3−δ (x ≥ 0.05) symmetrical cells reveal polarization resistances below 0.09 Ω cm² at 750 °C which are much smaller than that displayed by the pristine SrCoO_3−δ sample. The composition with x = 0.05 shows the lowest ASR values ranging from 0.009 to 0.23 Ω cm² in the 900-600 °C temperature interval with an activation energy of 0.82 eV.     

Novel layered perovskite GdBaCoFeO5+δ as a potential cathode for proton-conducting solid oxide fuel cells

While cobalt-containing perovskite-type cathode materials facilitate the activation of oxygen reduction, they also suffer from problems like poor chemical stability in CO₂, high thermal expansion coefficients, etc. Partial B site substitution with Fe element is expected to be able to mitigate these problems while keeping high catalyst performance. In this paper, a layered perovskite GdBaCoFeO_5+δ (GBCF) was developed as a cathode material for protonic ceramic membrane fuel cells (PCMFCs) based on proton-conducting electrolyte of stable BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY7). The button cells of Ni-BZCY7|BZCY7|GBCF were fabricated and tested from 600 to 700 °C with humidified H₂ (∼3% H₂O) as a fuel and ambient oxygen as oxidant. An open-circuit potential of 1.002 V, maximum power density of 482 mW cm⁻², and a low electrode polarization resistance of 0.11 Ωcm² were achieved at 700 °C. The experimental results indicated that the layered perovskite GBCF is a good candidate for cathode material, while the developed Ni-BZCY7|BZCY7|GBCF cell is a promising functional material system for intermediate temperature solid oxide fuel cells.     

SrCo0.7Fe0.2Ta0.1O3−δ perovskite as a cathode material for intermediate-temperature solid oxide fuel cells

Perovskite oxide SrCo_0.7Fe_0.2Ta_0.1O_3−δ (SCFT) was synthesized by a solid–state reaction and investigated as a potential cathode material for intermediate-temperature solid oxide fuel cell (IT-SOFC). The single phase SCFT having a cubic perovskite structure was obtained by sintering the sample at 1200 °C for 10 h in air. Introduction of Ta improved the phase stability of SCFT. The SCFT exhibited a good chemical compatibility with the La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ (LSGM) electrolyte at 950 °C for 10 h. The average thermal expansion coefficient was 23.8 × 10⁻⁶ K⁻¹ between 30 and 1000 °C in air. The electrical conductivities of the SCFT sample were 71–119 S cm⁻¹ in the 600−800 °C temperature range in air, and the maximum conductivity reached 247 S cm⁻¹ at 325 °C. The polarization resistance of the SCFT cathode on the LSGM electrolyte was 0.159 Ω cm² at 700 °C. The maximum power density of a single-cell with the SCFT cathode on a 300 μm-thick LSGM electrolyte reached 652.9 mW cm⁻² at 800 °C. The SCFT cathode had shown a good electrochemical stability over a period of 20 h short-term testing. These findings indicated that the SCFT could be a suitable alternative cathode material for IT-SOFCs.     

High-performance Ni–BaZr0.1Ce0.7Y0.1Yb0.1O3−δ (BZCYYb) membranes for hydrogen separation

Cermet membranes composited of Ni and doped barium cerate have been widely studied for hydrogen separation; however, their practical application is limited primarily by the relatively low permeation rate and instability of doped barium cerate in H₂O and CO₂ containing gases. Here we report our findings on the development of a thin-film cermet membrane consisting of Ni and BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3−δ (BZCYYb), supported on a porous Ni–BZCYYb substrate. High fluxes of 1.12 and 0.49 ml min⁻¹ cm⁻² have been demonstrated at 900 °C and 700 °C, respectively, when hydrogen was used as the feed gas on one side and N₂ as the sweep gas on the other side. Most importantly, the high-performance membrane can be easily fabricated by a cost-effective particle-suspension coating/co-firing process, offering great promise for large scale hydrogen separation applications.     

BaCo0.7Fe0.2Nb0.1O3−δ as cathode material for intermediate temperature solid oxide fuel cells

BaCo_0.7Fe_0.2Nb_0.1O_3−δ (BCFN) has been synthesized and characterized as cathode material for intermediate temperature solid oxide fuel cells (IT-SOFCs) using La_0.8Sr_0.2Ga_0.83Mg_0.17O_3−δ (LSGM) electrolyte. X-ray diffraction results show that pure cubic BCFN perovskite phase can be obtained at 950 °C through solid state reactions of BaCO₃, Co₃O₄, Fe₂O₃ and Nb₂O₅. The electrical conductivity of BCFN increases with the increase in oxygen partial pressure, indicating that BCFN is a p-type semiconductor. The polarization resistance of the BCFN cathode with LSGM electrolyte is only 0.06 Ω cm² at 750 °C in air under open-circuit conditions. The overpotential at a current density of 1 A cm⁻² in oxygen was only about 0.04 V at 750 °C. Peak power densities of 550, 770 and 980 mW cm⁻² have been achieved on LSGM-electrolyte supported single cells with the configuration of Ni-Gd_0.1Ce_0.9O_1.95|La_0.4Ce_0.6O₂|LSGM|BCFN at 700, 750 and 800 °C, respectively. These results indicate that BCFN is a very promising cathode candidate for IT-SOFCs with LSGM electrolyte.     

Investigation of cobalt-free perovskite Ba0.95La0.05FeO3−δ as a cathode for proton-conducting solid oxide fuel cells

Cobalt-free perovskite Ba_0.95La_0.05FeO_3−δ (BLF) was synthesized. The conductivity of BLF was measured with a DC four-point technique. The thermal expansion coefficient of the BLF was measured using a dilatometer. The BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY7) electrolyte based proton conducting solid oxide fuel cells (SOFCs) were fabricated. A composite cathode with BLF + BZCY7 was used to mitigate the thermal expansion mismatch with the BZCY7 electrolyte. The polarization processes of the button cell NiO-BZCY7/BZCY7/BLF + BZCY7 were characterized using the complicated electrochemical impedance spectroscopy technique. The open circuit voltage of 0.982 V, 1.004 V, and 1.027 V was obtained at 700 °C, 650 °C, and 600 °C, respectively, while the peak power density of 325 mW cm⁻², 240 mW cm⁻², and 152 mW cm⁻², was achieved accordingly.     

Novel BaCe0.7In0.2Yb0.1O3−δ proton conductor as electrolyte for intermediate temperature solid oxide fuel cells

Novel proton conductor BaCe_0.7In_0.2Yb_0.1O_3−δ (BCIYb) has been successfully synthesized by a modified Pechini method and characterized as electrolyte for intermediate temperature solid oxide fuel cells. Acceptable tolerance to wet CO₂ environment was found during chemical stability tests. No interaction between the BCIYb electrolyte and La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) cathode was observed during the cathode fabrication process. Further, no detectable impurity phase was found when the BCIYb-LSCF mixed powders were calcined at 700 °C for 50 h. BCIYb dense samples sintered at 1450 °C for 5 h showed acceptable conductivities of 7.2 × 10⁻³, 8 × 10⁻³, 4.5 × 10⁻³ and 3.1 × 10⁻³ S cm⁻¹ at 800 °C in dry air, wet air, wet H₂ and wet N₂, respectively. The maximum cell power outputs of single cells with the configuration of Ni-BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY)|BCIYb|BZCY-LSCF were 0.15, 0.218 and 0.28 W cm⁻² at 600, 650 and 700 °C, respectively. No cell degradation was observed for cells operated at a constant voltage of 0.7 V in the 25 h short-term durability test.     

Electrochemical performance of PrBaCo2O5+δ layered perovskite as an intermediate-temperature solid oxide fuel cell cathode

PrBaCo₂O_5+δ (PBCO) powder was prepared by a combined EDTA and citrate complexing method. The electrochemical performance of PBCO as a cathode for intermediate-temperature solid oxide fuel cells (IT-SOFCs) was evaluated. A porous layer of PBCO was deposited on a 42 μm thick electrolyte consisting of Ce_0.8Sm_0.2O_1.9 (SDC), prepared by a dry-pressing process. A fuel cell with a structure PBCO/SDC/Ni-SDC provides a maximum power density of 866, 583, 313 and 115 mW cm⁻² at 650, 600, 550 and 500 °C, respectively, using hydrogen as the fuel and stationary air as the oxidant. The total resistance of the cell was about 0.41, 0.51, 0.57 and 0.77 Ω cm², respectively. This encouraging data identifies PBCO as a potential cathode material for IT-SOFCs.     

Proton conducting solid oxide fuel cells with layered PrBa0.5Sr0.5Co2O5+δ perovskite cathode

BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY7) exhibits adequate protonic conductivity as well as sufficient chemical and thermal stability over a wide range of SOFC operating conditions, while layered perovskite PrBa_0.5Sr_0.5Co₂O_5+δ (PBSC) has advanced electrochemical properties. This research fully takes advantage of these advanced properties and develops a novel protonic ceramic membrane fuel cell (PCMFC) of Ni–BZCY7|BZCY7|PBSC. Experimental results show that the cell may achieve the open-circuit potential of 1.005 V, the maximal power density of 520 mW cm⁻², and a low electrode polarization resistance of 0.12 Ωcm² at 700 °C. Increasing operating temperature leads to the decrease of total cell resistance, among which electrolyte resistance becomes increasingly dominant over polarization resistance. The results also indicate that PBSC perovskite cathode is a good candidate for intermediate temperature PCMFC development, while the developed Ni–BZCY7|BZCY7|PBSC cell is a promising functional material system for SOFCs.     

BaZr0.2Ce0.8−xYxO3−δ solid oxide fuel cell electrolyte synthesized by sol–gel combined with composition-exchange method

This study reports the synthesis of proton-conducting BaZr_0.2Ce_0.8−xY_xO_3−δ (x = 0–0.4) oxides by using a combination of citrate-EDTA complexing sol–gel process and composition-exchange method. Compared to those oxides prepared from conventional sol–gel powders, the sintered BaZr_0.2Ce_0.8−xY_xO_3−δ pellets synthesized by sol–gel combined with composition-exchange method are found to exhibit improved sinterability, a higher relative density, higher conduction, and excellent thermodynamic stability against CO₂. Moreover, the Pt/electrolyte/Pt single cell using such a BaZr_0.2Ce_0.6Y_0.2O_3−δ electrolyte shows an obviously higher maximum powder density in the hydrogen-air fuel cell experiments. Based on the experimental results, we discuss the improvement mechanism in terms of calcined particle characteristics. This work demonstrates that the BaZr_0.2Ce_0.8−xY_xO_3−δ oxides synthesized by sol–gel combined with composition-exchange method would be a promising electrolyte for the use in H⁺-SOFC applications. More importantly, this new fabrication approach could be applied to other similar ABO₃-perovskite material systems.